Method for desulfurizing thiophene derivatives contained in fuels

ABSTRACT

The invention concerns a method for selectively desulphurizing thiopene compounds contained in hydrocarbons derived from crude oil distillation, whether refined or not, which consists in oxidising the thiophene sulphur atoms into sulphone in the presence of an oxidising agent and in separating said sulphonated compounds from said hydrocarbons. The invention is characterised in that it consists in oxidising the thiophene compounds in a two-phase turbulent medium comprising a hydrocarbon phase and an aqueous phase, in the presence of at least an oxidising agent soluble in at least one of the two phases and of at least a metal catalyst in soluble or dispersed form in a liquid of in solid form, separation and oxidation occurring simultaneously.

This invention relates to a method for desulfurizing fuels, namely gasoils, kerosenes and gasolines. In particular, it targets thedesulfurization of fuels that contain thiophene compounds.

The presence of sulfur in fuels is a problem considered today as a majorproblem for the environment. Indeed, the sulfur is converted, throughcombustion, into various sulfur oxides, that can transform into acids,thus contributing to the formation of acid rains.

In general, refineries use catalytic hydrodesulfurizing methods to lowerthe sulfur content of fuels. Thus, the gas oils that are deriveddirectly from the distillation are treated in reactors that operate attemperatures ranging between 300 and 400° C., a hydrogen pressure thatranges between 30 and 100.10⁵ Pa (between 30 and 100 bars) and hourlyspace velocities that range between 0.5 and 4 h⁻¹. The fuel's sulfurcompounds react with the hydrogen when in contact with the catalystarranged in a fixed bed and comprised of metal sulfides from groups VIand VIII supported on alumina, for example cobalt and molybdenumsulfides or nickel and molybdenum sulfides. Because of the operationalconditions and the consumption of hydrogen, these methods can be costlyboth in investments and in operation, and more so in cases where we seekto produce fuels with a very low sulfur content. Thus, to desulfurize afuel that initially contains 1% by weight of sulfur to a sulfur contentthat ranges between 0.05 and 0.005% by weight, the size of the reactorcan be multiplied by 4 and we must also increase the quantity ofhydrogen necessary for the reaction. We thus understand why it isparticularly difficult to eliminate traces of sulfur, in particular ifthe sulfur is contained in refractory molecules such as dibenzothiophenewith alkyl substituents in position 4, or 4 and 6.

In some countries, such as Sweden, the United States (in particular inCalifornia) and others, the total sulfur content of gas oils is alreadylimited to 0.005% by weight. This limitation could eventually become thestandard in the countries belonging to the OECD.

At the same time, in France, the total sulfur content in gasolines islimited to 0.05% by weight, but this limit could soon be lowered to0.005% by weight or less in 2005 and this for all of Europe.

Gasolines, as opposed to gas oils, are not only obtained through directdistillation, but also through various methods such as naphthareforming, light naphtha isomerization, the alkylation of butane orpropane that produce iso-octane, isobutene methoxylation and catalyticcracking of vacuum distillates or of atmospheric residues. Crackinggenerates between 20 and 60% by weight of the final gasoline and it isthe gasolines that are produced using this method that bring the sulfurcompounds into the gasoline, except for the low quantities of sulfurpresent in the direct distillation gasolines.

To desulfurize these cracked gasolines, usually methods similar to thosedescribed for the hydrodesulfurization of gas oils are used, where theoperational conditions for hydrogen pressure, space velocity andtemperature are stricter. Again, these methods are costly ininvestments, in operation and in hydrogen, because of the sulfurcontents we want to reach. It is however possible, using traditionalmanners, to reach total sulfur contents in said cracked gasolines thatrange between 0.005 and 0.03% by weight, based on the quantity oftreated hydrocarbons and the severity of the hydrotreating of saidhydrocarbons prior to the cracking step. In the absence ofhydrotreatment, the total sulfur content in the cracked gasoline couldreach up to 0.1% by weight. To reduce this sulfur content, additivesthat decompose the thiols and sulfurs that are formed in the gasolinethat is gathered can be added to the cracking catalyst. Unfortunately,these additives have little or no effect on the benzothiophenederivatives, even if hydrocarbons charged in the catalytic cracking unitwere previously hydrodesulfurized, meaning that the thiols and sulfurshave been removed.

One major disadvantage of the hydrodesulfurizing of cracked gasolines isthat, along with the desulfurizing, there is a partial hydrogenation ofthe olefins. Yet, said olefins are responsible for the good gasolineoctane number, and their disappearance results in a reduction of thisnumber, thus a lesser quality gasoline. To compensate for this loss,either other constituents that will improve this number can beintroduced, or the gasoline itself can be re-treated so as to increasethis number. As adding a new treatment or new compounds to the gasolinein order to improve the quality is also a burden on its cost price, weunderstand the advantage of a treatment method for desulfurizing thesulfur compounds, and more selectively, the benzothiophene compounds,that leaves the non sulfurized molecules intact and limits the use ofhydrogen.

The methods using selective oxidation of sulfur compounds can fulfillthis role. From the methods and procedures developed to reduce thequantity of sulfur present in fuels in the form of thiophenederivatives, oxidation by organic peroxides, organic hydroperoxides,hydrogen peroxide and organic peracids in the presence or in the absenceof catalysts based on organometallic compounds or metallic oxide, hasbeen considered (see U.S. Pat. No. 3,668,117, U.S. Pat. No. 3,565,793,EP 0 565 324 and publications by T. A. KOCH, K. R. KRAUSE, L. EMANZER,H. MEHDIZADEH, J. M. ODOM, S. K. SENGUPTA, New J. Chem., 1996, 20,163–173 and by F. M. COLLINS, A. R. LUCY, C. SHARP, J of MolecularCatalysis A: Chemical 117 (1997) 397–403).

For the methods that use molybdenum and tungsten based metal catalystsin the presence of hydrogen peroxide, operation temperatures are greaterthan 60° C. and there is an over consumption of hydrogen peroxide, aportion of this oxidizing agent being decomposed by the catalyst beingused. The use of peracids, very strong oxidizing agents obtained byreaction of hydrogen peroxide with a carboxylic acid such as formic acidor acetic acid, is very dangerous at these temperatures in hydrocarbonenvironments, because of the risk of explosion in the case of a shock orin the presence of light. Furthermore, they are less efficient thanhydrogen peroxide and less selective towards the sulfur compounds, sothat they can oxidize olefins.

In all these methods and procedures, thiophene derivatives aretransformed into their sulfonated and/or sulfonic form. However, forsome of these compounds, reaction even at high temperatures, isrelatively slow and the total conversion is not reached in less than onehour, unless very strong concentrations of oxidizing agents are used,often much higher than the quantities necessary for aquasi-stoichiometric oxidation of the sulfur derivatives.

Other methods of oxidation use phthalocyanines or metalpolyphthalocyanines in the presence of oxygen or ozone to transform thethiols and the H₂S contained in the oil products into organicdisulfides, as described, for example, in the U.S. Pat. Nos. 3,565,959and 3,039,855. However, such methods do not allow for the oxidization ofthe thiophene compounds that remain in the oil products. Furthermore,when applied to catalytic cracked gasolines, these methods favor theformation of fuel gums through the polymerization of the olefins, whichmakes the gasolines improper for use.

Therefore, the objective of this invention is to propose a method fordesulfurizing fuels that contain thiophene compounds without reducingthe octane number or the cetane number, sometimes even increasing them.In particular it relates to the finishing treatment of hydrotreated gasoils, kerosenes and catalytic cracking gasolines, with highconcentrations of thiophene compounds resistant to hydrogenations.

Therefore, the subject matter of this invention is a method forselectively desulfurizing the thiophene compounds contained in therefined or unrefined hydrocarbons derived from the crude oildistillation, comprising oxidizing the thiophene sulfur atoms intosulfone in the presence of an oxidizing agent, and separating saidsulfone compounds from said hydrocarbons, characterized in that thethiophene compounds are oxidized in a two-phase turbulent mediumcomprising a hydrocarbon phase and an aqueous phase, in the presence ofat least an oxidizing agent soluble in at least one of the two phasesand of at least one metal catalyst chosen from the metallicphtalocyanines, possibly substituted with alkyl groups comprising 1 to 4carbon atoms and/or sulfonic groups, and the catalysts comprising asupport selected from the group consisting of the silicas, aluminas,zirconias, amorphous or crystalline aluminosilicates, aluminophosphatesand mesoporous solids, alone or mixed with each other, possiblycomprising at least one metal selected from the group consisting oftitanium, zirconium, vanadium, chromium, molybdenum, iron, manganese,and tungsten, where said metals can be introduced into the network ofthe support or impregnated in complex form or non-complex form. Amongsaid catalysts, the non oxidized titanium catalysts are preferred.

The method as set forth in the invention has the advantage of allowingfor a selective oxidation of the thiophene sulfur into sulfone. Theseparation of the sulfones from the hydrocarbons is immediate, thelatter passing into the aqueous phase. Furthermore, this oxidation hasno effect on the olefins, the octane number or the non-sulfurizedaromatic compound content of the catalytic cracking gasoline thusremaining unchanged. Furthermore, the oxidation method as set forth inthe invention improves the cetane number of the gas oils.

These specific effects are linked to the synergy effect of the selectedoxidizing agents and the catalysts used.

Thus, in the context of this invention, the oxidizing agent is chosenfrom the group consisting of organic peroxides, hydrogen peroxide,organic hydroperoxides, peracids and alkaline and alkaline-earthpersulfates.

To complete the extraction, meaning the passing of the sulfonatedthiophene compounds from the hydrocarbon phase to the aqueous phase andaccelerate the oxidation reaction, to the two-phase reaction medium, asolvent miscible with water and hardly miscible with hydrocarbons,chosen from the group consisting of alkanols that contain from 1 to 4carbon atoms, acetonitrile, dimethyl formamide, nitromethane,nitrobenzene, is added to the two-phase reaction medium in awater/solvent ratio ranging between 1/99 and 99/1 and preferably between25/75 and 75/25. To recuperate the sulfonated compounds derived from theoxidation reaction, one could also proceed using distillation and/orabsorption on a refractory oxide of the alumina or silica type, and/orprecipitation of said oxidized compounds, based on known procedures,such as described in the European patents 0 585 324 and 0 482 841.

In a preferred embodiment of the method set forth in the invention, themetal catalyst (expressed in metal)/oxidizing agent molar ratio variesbetween 1/10⁵ and 100/1 in the two-phase reaction medium, the reactiontemperature ranges between the ambient temperature and 90° C., andpreferably between 50 and 90° C., under atmospheric pressure, and theaqueous solution's pH it maintained below 12 and preferably between 4and 9.

In a particular embodiment of the invention, from the metal catalystsconsisting of metal phthalocyanines, the iron phthalocyanines, possiblysubstituted with alkyl groups comprised of 1 to 4 carbon atoms and/orsulfone groups, in an aqueous solution or supported on a solid phasechosen from the refractory metal oxides group such as alumina, zirconia,silica, tungstate, clays and organic resins such as cationic resinsfunctionalized with ammonium groups are preferred. In this embodiment,the metal phthalocyanines are not substituted with sulfonic groups andcan be linked to the support by ionic or covalent links of thesulfonamide type.

When the metal catalyst is a non oxidized titanium catalyst, titaniumzeolites, without extra-network titanium, with a pore diameter of atleast 0.65 nm, and titanium mesoporous composites, and more particularlytitanium beta zeolite are preferred. Said zeolites can be prepared byimplementing the method described in the European patent 0 842 114.

In this particular embodiment of the invention, the metal catalyst(expressed in metal) oxidizing agent molar ratio varies from 1/10 to1/40 in the two-phase reaction medium.

According to the invention, the oxidizing agents are chosen from thecompounds with a general formula of R₁OOR₂, where R₁ and R₂ areidentical or different, chosen from hydrogen and linear or branchedalkyl groups, comprised of 1 to 30 carbon atoms.

In a preferred embodiment, the oxidizing agent whose formula is R₁OOR₂is chosen from the group consisting of hydrogen peroxide, terbutylhydroperoxide and terbutylperoxide. The preferred oxidizing agents areterbutylperoxide and hydrogen peroxide, where the latter is greatlypreferred because of its low pollution effect.

Other oxidizing agents of the invention, i.e. peracids of formulaR₃COOOH₂ are chosen so that R₃ is hydrogen or a linear or branched alkylgroup consisting of 1 to 30 carbon atoms. They are preferably chosenfrom the group consisting of peracetic acid, performic acid andperbenzoic acid. To avoid any problems with explosions, they are formedin situ by progressively adding a small quantity of a hydrogenperoxide/carboxylic acid mix.

No matter which oxidizing agent and catalyst are used, the aqueoussolution/hydrocarbons mass ratio varies from 10/1 to 1/1. Preferably wewill operate with a ratio that varies from 2/1 to 1/5.

A second subject matter of the invention is the application of themethod as defined above to the specific finishing treatment of thegasolines derived from catalytic cracking or to the treatment of gasoils that have been previously hydrotreated and kerosenes, so the methodis more economical.

The object of the examples hereafter is to illustrate the efficiency ofthe method as set forth in the invention, without limiting its scope.

In these examples, we will refer to FIGS. 1 and 2 of the attacheddrawings, that will be explained in Examples I and V respectively.

EXAMPLE I

The object of this example is to show the activity of the metalphthalocyanine/hydrogen peroxide combination with regard to theoxidation of the thiophene derivatives present in fuels, mainlybenzothiophene (BT), dibenzothiophene (DBT) and dimethyldibenzothiophene4.6 (DMBT).

The metal phthalocyanines used are iron sulfophthalocyanines (FePcS),cobalt sulfophthalocyanines (CoPcS) and nickel sulfophthalocyanines(NiPcS). Test were carried out in an organo (acetonitrile/water)aqueoustwo phase medium with a pH of 7.7, where the oxidizing agent metalphthalocyanine ratio is 20/1, the temperature is the ambient temperatureof 20° C. and the pressure is the atmospheric pressure and the mixtureis agitated.

As comparison tests and to show the efficacy of the catalyst, oxidationof the same thiophene derivates is carried out, on the one hand, in thepresence of a catalyst comprised of a zeolite TS-1 (zeolites whose porediameter is less than 0.6 nm) and hydrogen peroxide H₂O₂ and, on theother hand, in the presence of iron phthalocyanine and atmosphericoxygen.

The thiophene derivatives to be oxidized are introduced into theacetonitrile at 1 mmole/l. Table 1 hereafter shows the results inpercentage of oxidation obtained after 30 minutes of reaction.

TABLE 1 Oxidizing Agent Catalyst / Concen- Oxidizing tration % sulfoneoxidation Agent (eqS) BR (1 mM) DBT (1 mM) DMBT(1 mM) H₂O₂ 2 3 <1 <1FePcS (air) 0 0 0 FePcS/H₂O₂ 2 90 95 95 FePcS/H₂O₂ 3 100 100 100CoPcS/H₂O₂ 2 <1 <1 <1 NiPcS/H₂O₂ 2 <1 <1 <1 TS-1/H₂O₂ 2 0 0 0

FIG. 1 is a curve that illustrates the evolution of the DBT(dibenzothiophene) content remaining in the acetonitrile/water two-phasemedium based on time.

At room temperature and atmospheric pressure, the oxidation of thethiophene derivatives by the peroxides alone or by the sulfonated metalphthalocyanine alone in an aerated medium is ineffective.

However, the iron phthalocyanines/peroxide couples catalyze theoxidation of the thiophene BT, DBT and DMBT derivatives into sulfonevery effectively. Note that the DMBT, a substrate that is difficult tooxidize because of the steric hindrance of the methyl groups in positionβ of sulfur is oxidized as quickly as the DBT.

On the contrary, the cobalt and nickel sulfophthalocyanines, as well asthe TS-1 are inefficient for such an oxidation under the conditions ofthe reaction.

EXAMPLE II

The object of this example is to present the oxidation of thedibenzothiophene in a liquid/liquid two-phase catalyst system, bychoosing heptane as the solvent for the organic phase. The aqueous phaseconsists of pH7.7 buffer consisting of phosphate and acetone, so as tosolubilize the iron sulfophthalocyanine and a minimum of DBT (initialpartition of the DBT 95:5, organic phase/aqueous phase).

We operate under the following conditions:

DBT: 1 mmol/l; FePcS 0.1 mmol/l; H₂O₂: added continuously 5 eq/h;temperature: 20° C.; atmospheric pressure; magnetic agitation.

Under the reaction conditions being used, the catalyzed oxidation of DBTis complete after 30 minutes of reaction, i.e. after adding 2.5equivalents of H₂O₂. The DBT is entirely converted into thecorresponding sulfone that is stable with regard to the oxidizing systemused and partitions between the two phases (final ratio of the sulfone1/3, organic phase/aqueous phase).

EXAMPLE III

This example relates to oxidation in a three-phase mixture, when thecatalyst is a non oxidized titanium catalyst in a solid dispersed formin the two-phase reaction mixture. Two types of catalyst were tested:Ti-beta (zeolite with a BEA structure) and Ti-HMS (titanium mesoporouscomposite). The Ti-beta (without extra-network titanium) was obtainedfrom a post-treated commercial zeolite as set forth in the proceduredescribed in the European patent 0 842 114.

The titanium mesoporous composite was obtained by co-precipitation, in ahighly acid medium, of silicate and titanium oxide, in the presence of apluronic type non ionic surfactant.

The catalyst' main characteristics are presented in Table 2 hereafter.

TABLE 2 Ti/(Ti + Si) BET surface Diameter of Vmp Catalyst mole/mole m²/gparticles, μ (ml/g) Ti-beta 0.008 470 0.3 0.28 Ti-HMS 0.024 838 10 0.42

The oxidizing agent used is hydrogen peroxide. The fraction to beoxidized is a benzothiophene and dibenzothiophene solution in n-decane.The reaction medium containing 0.5 mmole of benzothiophene, 0.5 mmole ofdibenzothiophene, 20 ml of n-decane, 1 ml of aqueous solution containing30% by weight of hydrogen peroxide, 100 mg of catalyst and 20 ml of asolvent non miscible in n-decane that can be an alcohol, acetonitrile orwater are introduced into a 60 ml reactor. The medium is vigorouslyagitated using a magnetic agitator and is maintained at a temperature of70° C. (or 64.5° C. if methanol is the solvent) at atmospheric pressure.

After the reaction, the hydrocarbon and aqueous phases are separated bysimple decantation.

The conversions of the sulfur compounds are presented in Table 3 below,after five hours of reaction.

TABLE 3 Conversion % Catalyst Solvent Benzothiophene DibenzothiopheneTi-HMS Acetonitrile 56.0 67.0 Ti-beta Methanol 100 93.7 Ti-betaAcetonitrile 96.7 91.0 Ti-beta Water 64.3 25.0

We notice from these results that both catalysts are efficient inoxidizing thiophenes. The efficiency of the solvent is linked to thesolubility of the oxidation products. Thus, they are much more solublein methanol and acetonitrile than in water.

EXAMPLE IV

The object of this example is oxidation in a three-phase mixture whenthe catalyst is not a titanium catalyst. We operate as described inExample III.

Among the catalysts used in this example, the HMS mesoporous solid basedcatalysts are obtained by co-precipitation in a highly acidic medium, ofsilicate and vanadium, tungsten, or molybdenum oxide, in the presence ofa non ionic surfactant of the pluronic type.

The alumina or zirconia based catalysts are obtained by impregnation bywet process of ammonium metatungstate or vanadate in an aqueoussolution, followed by drying and lastly calcination at 500° C.

Table 4 hereafter presents the results obtained with these catalysts.

TABLE 4 Conversion, % Catalyst Solvent Benzothiophene DibenzothiopheneV-HMS Methanol 40.0 45.0 V-HMS Acetonitrile 51 55 Mo-HMS Acetonitrile 3236 W-HMS Acetonitrile 20 27

It is obvious, from this table and the previous example, that theefficiency of the desulfurizing of the dibenzothiophene derivativesdepends greatly on the compromise, the nature of the support, the natureof the metal and the nature of the extraction solvent of the sulfonesthat are formed. Under the operational conditions of Example III,titanium catalysts seem to be the most efficient.

EXAMPLE V

The object of this example it to describe the oxidation kinetic ofsulfur compounds contained in kerosene. The catalyst being used isTi-beta, whose characteristics are presented in Example III. Thefraction being treated is a kerosene that contains 1310 ppm of sulfur,present in most sulfur compounds in the form of thiophene compounds.

The reaction medium containing 40 ml of kerosene, 0.35 ml of aqueoussolution at 30% by weight of hydrogen peroxide, 1 g of catalyst and 20ml of acetonitrile is introduced into a 100 ml reactor. The medium isvigorously agitated using a magnetic agitator and is maintained at atemperature of 60° C., at atmospheric pressure. The kerosene is thenwashed using acetonitrile to finish the separation before measuring thetotal sulfur content.

The kerosene desulfurization rate based on the reaction time ispresented in FIG. 2.

We note from this figure that after 2 hours, 90% of the sulfur iseliminated. The oxidized sulfur compounds pass fully in the phase thatcontains the acetonitrile and water.

EXAMPLE VI

The object of this example is oxidation in a three-phase mixture whenthe catalyst is a non oxidized titanium catalyst in its dispersed solidform in the two-phase reaction mixture. Two types of catalyst weretested: Ti-beta and Ti-HMS, whose characteristics are presented inExample III.

The fraction being treated is kerosene that contains 1310 ppm of sulfur,for the most part in the form of thiophene compounds.

The reaction medium consisting of 40 ml of hydrocarbons, 2 ml of aqueoussolution (30% gr) of hydrogen peroxide, 200 mg of catalyst and 20 ml ofa solvent that is not miscible with hydrocarbons, that may be analcohol, acetonitrile or water is introduced into a 100 ml reactor. Themedium is vigorously agitated using a magnetic agitator and ismaintained at a temperature of 70° C., at atmospheric pressure.

After the reaction, the three phases (kerosene, solvent+water, catalyst)were separated by filtration and decantation. No other operation wascarried out on the fractions before they were analyzed.

The efficiency of the catalysts taken in the presence of hydrogenperoxide is measured by the decrease of sulfur in the supernatanthydrocarbonated phase. The results are provided in Table 5 hereafter.

TABLE 5 Reaction Phase being Sulfur, % sulfur Catalyst Solvent time (h)analyzed ppm eliminated Acetonitrile Extraction Kerosene 1220 7.0 Ti-HMSAcetonitrile 9 Kerosene 190 85.5 9 MeCN 2500 Ti-beta Acetonitrile 5Kerosene 80 94.0 5 MeCN 2300 Ti-beta Ethanol 5 Kerosene 390 70.2 10 30077.00 24 250 81.0 24 Kerosene 80 94.0 washed in acetonitrile 24 EtOH1800 Ti-beta H₂O 10 Kerosene 840 86.0 10 Kerosene 300 77.1 washed inacetonitrile 10 H₂O 450

We note, from this table, that both catalysts are just as efficient inoxidizing the sulfur in the present kerosene. The oxidation products(sulfones) are not very soluable in hydrocarbons and they pass into thesolvent. The efficiency of the solvent is linked to the solubility ofthe sulfones: acetonitrile>ethanol>water.

1. Method of selective desulfurizing of thiophene compounds contained inrefined or unrefined hydrocarbons derived from the distillation of crudeoil, comprising: oxidizing thiophene sulfur atoms into sulfone in thepresence of an oxidizing agent; and separating the sulfone compoundsfrom said hydrocarbons, characterized in that the thiophene compoundsare oxidized in a two-phase turbulent phase consisting of a hydrocarbonphase and an aqueous phase, in the presence of at least one oxidizingagent soluble in at least one of the two phases, the oxidizing agentbeing selected from the group consisting of organic peroxides, hydrogenperoxide, organic hydroperoxides, peracids, alkaline persulfates, andalkaline earth persulfates, and in the presence of at least one metalcatalyst selected from the group consisting of (1) metal phthalocyaninesand (2) catalysts comprising (i) a support selected from the groupconsisting of silicas, aluminas, zirconias, amorphous or crystallinealuminosilicates, aluminophosphates, mesoporous solids, and mixturesthereof, and (ii) at least one metal selected from the group consistingof titanium, zirconium, vanadium, chromium, molybdenum, iron, manganeseand tungsten, where said metal (ii) can be introduced into the supportnetwork or impregnated in complex or non complex form, wherein theseparation and the oxidation occur simultaneously, and wherein theaqueous solution pH is kept under
 12. 2. Method as set forth in claim 1,characterized in that an extraction solvent selected from the groupconsisting of alcanols comprised of 1 to 4 carbon atoms, acetonitrile,formamide dimethyl, nitromethane, and nitrobenzene is added to thetwo-phase reaction medium, in a water/solvent ratio ranging between 1/99and 99/1.
 3. Method as set forth in claim 1, characterized in that themetal catalyst (expressed in metal)/oxidizing agent molar ratio rangesbetween 1/10⁵ and 100/1, and in that the reaction starts at ambienttemperature and atmospheric pressure.
 4. Method as set forth in claim 1,characterized in that the metal phthalocyanine is an ironphthalocyanine.
 5. Method as set forth in claim 1, characterized in thatthe metal phthalocyanine is an iron phthalocyanine supported over asolid phase selected from the group consisting of refractory metaloxides, clays and organic resins.
 6. Method as set forth in claim 1,characterized in that the oxidizing agent is a compound with a generalformula of R₁ ^(OOR) ₂, where R₁ and R₂ are independently selected fromthe group consisting of hydrogen and linear or branched alky groupshaving 1 to 30 carbon atoms.
 7. Method as set forth in claim 6,characterized in that the oxidizing agent is selected from the groupconsisting of hydrogen peroxide, terbutyl hydroperoxide and terbutylperoxide.
 8. Method as set forth in claim 6, characterized in that theoxidizing agent is hydrogen peroxide.
 9. Method as set forth in claim 1,characterized in that the oxidizing agent is a peracid with a formula ofR₃COOOH, where R₃ is hydrogen or a linear or branched alkyl groupcomprised of 1 to 30 carbon atoms.
 10. Method as set forth in claim 9,characterized in that the oxidizing agent is selected from the groupconsisting of peracetic acid, performic acid and perbenzoic acid. 11.Method as set forth in claim 1, characterized in that the aqueoussolution/hydrocarbon mass ratio ranges between 10/1 and 1/10.
 12. Methodas set forth in claim 1, wherein the hydrocarbons are selected from thegroup consisting of hydrotreated gas oils, kerosenes and gasolines. 13.Method as set forth in claim 1, wherein the metal phthalocyanines aresubstituted by alkyl groups consisting of 1 to 4 carbon atoms and/orsulfonic groups.
 14. Method as set forth in claim 2, wherein thewater/solvent ratio ranges between 25/75 and 75/25.
 15. Method as setforth in claim 3, wherein the aqueous solution pH ranges between 4 and9.
 16. Method as set forth in claim 4, wherein the iron phthalocyanineis substituted by alkyl groups comprised of 1 to 4 carbon atoms and/orsulfonic groups in an aqueous solution.
 17. Method as set forth in claim5, wherein the iron phthalocyanine is substituted by alkyl groupscomprised of 1 to 4 carbon atoms and/or sulfonic groups, the refractorymetal oxides are selected from the group consisting of alumina,zirconia, silica, and tungstate, and the organic resins are cationicresins functionalized by ammonium groups.
 18. Method as set forth inclaim 11, wherein the aqueous solution/hydrocarbon mass ratio rangesbetween 2/1 and 1/5.
 19. Method as set forth in claim 12, wherein thegasolines are gasolines derived from catalytic cracking.
 20. Method ofselective desulfurizing of thiophene compounds contained in refined orunrefined hydrocarbons derived from the distillation of crude oil,comprising: oxidizing thiophene sulfur atoms into sulfone in thepresence of an oxidizing agent; and separating the sulfone compoundsfrom said hydrocarbons, characterized in that the thiophene compoundsare oxidized in a two-phase turbulent phase consisting of a hydrocarbonphase and an aqueous phase, in the presence of at least one oxidizingagent soluble in at least one of the two phases, the oxidizing agentbeing selected from the group consisting of organic peroxides, hydrogenperoxide, organic hydroperoxides, peracids, alkaline persulfates, andalkaline earth persulfates, and in the presence of at least one metalcatalyst selected from the group consisting of (1) metal phthalocyaninesand (2) catalysts comprising (i) a support selected from the groupconsisting of silicas, aluminas, zirconias, amorphous or crystallinealuminosilicates, aluminophosphates, mesoporous solids, and mixturesthereof, and (ii) at least one metal selected from the group consistingof titanium, zirconium, vanadium, chromium, molybdenum, iron, manganeseand tungsten, where said metal (ii) can be introduced into the supportnetwork or impregnated in complex or non complex form, characterized inthat the metal catalyst is a titanium catalyst selected from the groupconsisting of titanium zeolite without extra-network titanium, with apore diameter greater than or equal to 0.65 nm and titanium mesoporouscomposites, and wherein the separation and the oxidation occursimultaneously.
 21. Method as set forth in claim 20, characterized inthat the metal catalyst (expressed in metal)/oxidizing agent molar ratiovaries from 1/10 to 1/40.
 22. Method as set forth in claim 20, whereinthe titanium zeolite is titanium beta zeolite.
 23. Method of selectivedesulfurizing of thiophene compounds contained in refined or unrefinedhydrocarbons derived from the distillation of crude oil, comprising:oxidizing thiophene sulfur atoms into sulfone in the presence of anoxidizing agent; and separating the sulfone compounds from saidhydrocarbons, characterized in that the thiophene compounds are oxidizedin a two-phase turbulent phase consisting of a hydrocarbon phase and anaqueous phase, in the presence of at least one oxidizing agent solublein at least one of the two phases, the oxidizing agent being selectedfrom the group consisting of organic peroxides, hydrogen peroxide,organic hydroperoxides, peracids, alkaline persulfates, and alkalineearth persulfates, and in the presence of at least one metal catalystselected from the group consisting of (1) metal phthalocyanines and (2)catalysts comprising (i) a support selected from the group consisting ofsilicas, aluminas, zirconias, amorphous or crystalline aluminosilicates,aluminophosophates, mesoporous solids, and mixtures thereof, and (ii) atleast one metal selected from the group consisting of titanium,zirconium, vanadium, chromium, molybdenum, iron, manganese and tungsten,where said metal (ii) can be introduced into the support network orimpregnated in complex or non complex form, wherein the separation andthe oxidation occur simultaneously, and wherein the metal catalyst is anon-oxidized titanium catalyst.